CN106756871A - A kind of Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure and its growth in situ method - Google Patents
A kind of Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure and its growth in situ method Download PDFInfo
- Publication number
- CN106756871A CN106756871A CN201611019332.XA CN201611019332A CN106756871A CN 106756871 A CN106756871 A CN 106756871A CN 201611019332 A CN201611019332 A CN 201611019332A CN 106756871 A CN106756871 A CN 106756871A
- Authority
- CN
- China
- Prior art keywords
- substrate
- transition
- source
- growth
- metal dichalcogenide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure and its growth in situ method.Method includes：Step A：Substrate, source material I, source material II and carbon source are provided respectively; substrate is heated up; carbon source is set to be dissolved into the surface of substrate under protective atmosphere; source material I and source material II are heated volatilization respectively, further deposit and react on the surface of the substrate for being dissolved with carbon and generate a kind of Transition-metal dichalcogenide two-dimensional material；Step B：Control substrate is lowered the temperature with certain rate of temperature fall, in Transition-metal dichalcogenide two-dimensional material and the interface indigenous graphite alkene of substrate, so as to obtain a kind of Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure.The window of conditional parameter is wider, reproducible needed for this method growth, is to prepare Transition-metal dichalcogenide two dimension material-Graphene related microelectronic component the later stage to have laid a good foundation.
Description
Technical field
The present invention relates to two-dimensional material preparing technical field, relate more specifically to a kind of Transition-metal dichalcogenide two dimension
Material-Graphene heterojunction structure and its growth in situ method.
Background technology
Since being found from Graphene in 2004, other New Two Dimensional crystalline materials always two-dimensional material research neck has been sought
The forward position in domain.As Graphene, other two dimensional crystals of large-size high-quality are not only for new under the two-dimentional limit of exploration
Physical phenomenon and performance are extremely important, and have the application of many novelties in fields such as electronics, photoelectrons.In recent years, except stone
Outside black alkene, the two-dimensional material such as two-dimentional hexagonal boron nitride, Transition-metal dichalcogenide two-dimensional material, black phosphorus is also prepared out,
It is greatly expanded performance and the application of two-dimensional material.
The excellent performance of Transition-metal dichalcogenide two-dimensional material be conducive to it nanoelectronics, photoelectronics and from
Widely apply in rotation electronics etc. field, it is considered to be one of mole epoch critical material afterwards.Except similar to electronics and photoelectricity
This important application of device, two-dimensional material is also applied in various functionalization devices.In in the past few years, by different two-dimentional materials
The heterojunction structure that stockpile is folded shows huge potentiality again in device design with application direction, based on these heterojunction structures
Research can be used to prepare various functions device, such as field-effect transistor, logic inverter and photodetector etc..And graphite
Alkene is different, and Transition-metal dichalcogenide two-dimensional material possesses certain band gap and band gap is relevant with the number of plies, its spin(-)orbit
Coupling effect combines unique crystal symmetry and produces many interesting light, electricity, magnetic phenomenons.These superior properties are in photoelectricity
Favored and confirmed in the fields such as device.By the high carrier mobility of Graphene and good electron conduction and transition metal
It is to prepare Transition-metal dichalcogenide two-dimensional material-stone that the excellent photoelectric properties of chalcogenide two-dimensional material complement each other
The original intention of black alkene heterojunction structure.
The method being by mechanically pulling off can prepare high-quality graphene film and Transition-metal dichalcogenide two
Dimension material film and its heterojunction structure.However, mechanical stripping method high cost, efficiency are low, universal smaller, the pole of heterojunction structure of preparation
The earth limits its application in devices field.Chemical vapor deposition (CVD) method is that batch prepares individual layer and multi-layer graphene
And a kind of effective means of Transition-metal dichalcogenide two-dimensional material domain and continuous film.At present, by chemical vapor deposition
Method has prepared graphene film and Transition-metal dichalcogenide two on the transition metal such as Cu, Ni, Au and Pt
Dimension material film, but the interface pollution brought of associated transitions technology makes it be difficult to meet it the need for devices field application.
It is still section that Graphene-Transition-metal dichalcogenide two-dimensional material heterojunction structure is directly prepared by the way of growth in situ
Learn the big difficult point in research.
The content of the invention
It is an object of the invention to provide a kind of Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure and its
Growth in situ method, so as to solve the Transition-metal dichalcogenide two-dimensional material-Graphene hetero-junctions for preparing in the prior art
Structure area is small, poor controllability and because chemistry transfer etc. ex situ growing method cause interface pollution the problems such as.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
According to the first aspect of the invention, there is provided a kind of Transition-metal dichalcogenide two-dimensional material-Graphene hetero-junctions
The growth in situ method of structure, including：Step A：Substrate, source material I, source material II and carbon source are provided respectively, first will be described
Substrate heats up, and the carbon source is dissolved into the surface of the substrate under the atmosphere of protective gas, then the source material I and source
Material II is heated volatilization respectively, is further deposited on the surface of the substrate for being dissolved with carbon and reacts a kind of transition metal of generation
Chalcogenide two-dimensional material；And step B：The substrate is controlled to be lowered the temperature with certain rate of temperature fall, in the transition
The interface indigenous graphite alkene of metal chalcogenide compound two-dimensional material and the substrate, so as to obtain a kind of transition metal sulfur family
Compound two-dimensional material-Graphene heterojunction structure.
Wherein, the step A is specifically included：A1：Cleaning substrate, weighs the source material I and source material of certain mass respectively
II；A2：The substrate, source material I, source material II are respectively put into each heating zone of heated type chemical vapor deposition chamber
In, it is 550-1100 DEG C to keep the substrate temperature, after being passed through carbon source, high annealing 1min~60min；And A3：By institute
State source material I and be separately heated to 100~300 DEG C and 500~950 DEG C with the source material II, while being passed through protective gas 5min
~60min, generates the Transition-metal dichalcogenide two-dimensional material.
Wherein, in above-mentioned steps A2, when being passed through carbon source, source material I and the place warm area of source material II are maintained at transition gold
Below source volatilization temperature when category chalcogenide two-dimensional material grows.
The substrate is selected from the metal or alloy for possessing certain molten carbon ability.
Preferably, the substrate is selected from the one kind in Co, Ni, Pt, Mo, W, Pd or Ta.
The source material I is selected from one or more in the gas, liquid, solid state source containing S, Se, Te, and the source material II is selected from
One or more in gas, liquid, solid state source containing Mo, W, Ta, Ga, Sn, Re.
The carbon source is selected from one or more in carbon containing gas, liquid, solid source.
Preferably, the carbon source is selected from one or more in methane, ethane, ethene, acetylene.
The step B is specifically included：Heating zone where the substrate is controlled under the atmosphere of the protective gas is with 1
DEG C/rate of temperature fall of s-20 DEG C/s lowered the temperature, in the temperature-fall period, in the Transition-metal dichalcogenide two-dimensional material
With the interface indigenous graphite alkene of the substrate.
In step A and step B, the protective gas is argon gas and hydrogen or the mixed gas of helium and hydrogen, institute
The volume ratio for stating mixed gas is 0.2:1~20:1.
Wherein, in step, when multi-temperature zone heats up, chemical vapor deposition chamber keeps low pressure or condition of normal pressure, preferably
, the low pressure is 500~10000Pa.
Wherein, in stepb, when multi-temperature zone is lowered the temperature, chemical vapor deposition chamber keeps normal pressure or lower pressure.
According to the second aspect of the invention, also provide a kind of using the transition being prepared from according to above-mentioned growth in situ method
Metal chalcogenide compound two-dimensional material-Graphene heterojunction structure.
The Transition-metal dichalcogenide two-dimensional material is individual layer domain, multilayer domain or continuous film, the graphite
Alkene is individual layer domain, multilayer domain or continuous film.
Wherein, the domain of the Transition-metal dichalcogenide two-dimensional material is mainly deposited on graphenic surface, transition gold
Category chalcogenide two-dimensional material-Graphene heterogenous multilayer structure is in pyramid pattern, and there is interlayer strict stacking to close
System.
First, present invention greatest improvement compared with the prior art be can be disposably real by chemical vapor deposition growth
The growth of existing Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure, and former method is by after growth
What transfer or twice growth course were completed.
Secondly, method disclosed by the invention overcomes the Graphene regrowth transition metal sulfur family long of Mr. in the prior art
In the method for compound two-dimensional material, for the etching of Graphene, the present invention is in Transition-metal dichalcogenide two dimension for high temperature sulphur source
Material growth terminate after just indigenous graphite alkene, it is to avoid the Quality Down that Graphene is etched and causes.
Compared with prior art, the invention has the advantages that：
The present invention prepares large scale Transition-metal dichalcogenide two dimension by chemical gaseous phase depositing process in substrate surface
Material-Graphene heterojunction structure, preparation condition is simple, low cost, solves and prepare in the prior art transition metal sulfur family chemical combination
Thing two-dimensional material-Graphene heterojunction structure area is small, poor controllability, because of boundaries for causing of ex situ growing method such as chemistry transfers
The problems such as face is polluted, is Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure answering in fields such as photoelectric devices
With laying a good foundation.
Brief description of the drawings
Fig. 1 be the present invention with methane as gaseous carbon source, be source material with two kinds of Solid Sources, Transition Metal Sulfur is prepared with substrate
The schematic device of compounds of group two-dimensional material-Graphene heterojunction structure；
Fig. 2 is the typical SEM pictures of the molybdenum bisuphide-Graphene heterojunction structure prepared according to embodiment one；
Fig. 3 a are that the molybdenum bisuphide-Graphene heterojunction structure prepared according to embodiment one is transferred to 300nm SiO2/ Si is served as a contrast
Optical microscope picture after on bottom；
Fig. 3 b are the Raman spectral lines of solid black circle labeling position in Fig. 3 a；
Fig. 4 is the typical SEM pictures of the molybdenum bisuphide-Graphene heterojunction structure prepared according to embodiment two；
Fig. 5 a, 5b are respectively A1g the and E2g Raman Mapping of the molybdenum bisuphide domain prepared according to embodiment two
Figure；
Fig. 6 is the typical SEM pictures of the two selenizing molybdenums-Graphene heterojunction structure prepared according to embodiment three；
Fig. 7 a are that the two selenizing molybdenums-Graphene heterojunction structure prepared according to embodiment three is transferred to 300nm SiO2/ Si is served as a contrast
Optical microscope picture after on bottom；
Fig. 7 b are the Raman spectral lines that solid black shown in Fig. 7 a justifies labeling position；
Fig. 8 is the typical SEM pictures of the tungsten disulfide-Graphene heterojunction structure prepared according to example IV；
Fig. 9 a are that the tungsten disulfide-Graphene heterojunction structure prepared according to example IV is transferred to 300nm SiO2/ Si is served as a contrast
Optical microscope picture after on bottom；
Fig. 9 b are the Raman spectral lines that solid black shown in Fig. 9 a justifies labeling position；
Figure 10 a, 10b, 10c are respectively the allusion quotations of the molybdenum bisuphide-amorphous carbon film heterojunction structure prepared according to comparative example one
Type SEM pictures, grey filled circles and solid black justify the Raman spectral lines of labeling position；
Figure 11 is the typical SEM pictures of the molybdenum bisuphide-Graphene heterojunction structure prepared according to comparative example two；
Figure 12 a, 12b, 12c are respectively typical SEM pictures, the grey filled circles of the molybdenum bisuphide prepared according to comparative example three
And solid black justifies the Raman spectral lines of labeling position.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.It should be understood that following examples are merely to illustrate this
Invention is not for limitation the scope of the present invention.
Preferably to be contrasted and being analyzed, the listed embodiment of the present invention is using transition metal oxide source as source thing
Matter II, Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure is prepared by chemical vapor deposition manner, and Fig. 1 is
The schematic diagram of its exemplary device.Optionally, also can using the Solid Source such as transition metal chloride, because of chemical vapor deposition method and
Its equipment therefor is well known to the skilled person, therefore will not be repeated here.
Embodiment one
First, substrate is cleaned.In the present embodiment, from the molybdenum foil that thickness is 25 μm as substrate.First, with acetone and different
Propyl alcohol is each cleaned by ultrasonic 10min, then with deionized water drip washing substrate surface, with 5% dilute hydrochloric acid drip washing substrate surface,
Deionized water drip washing substrate surface is used again, is afterwards dried up the substrate after cleaning with nitrogen gun.
Then, two introduces a collection materials are weighed.Source material I and source material II select S sources and MoO respectively in the present embodiment3Source.Its
In, S sources are 300mg, MoO3Source is 10mg.
Then, the molybdenum foil substrate after the source material I, source material II and the cleaning that will weigh is respectively placed in the change shown in Fig. 1
Learn in heating zone I, heating zone II, the heating zone III of vapor deposition chamber, anneal 30min at 150 DEG C, anneal under 200Pa
Carry out, the protective gas of selection is argon gas and hydrogen, is passed through from air inlet, is flowed out from gas outlet, its velocity ratio Ar:H2=
10:1.After annealing terminates, the air pressure of chemical vapor deposition chamber is first switched into normal pressure, then by heating zone III where molybdenum foil substrate
It is warming up to 750 DEG C and maintains constant temperature.Gaseous carbon source 15min is passed through under protective gas atmosphere simultaneously, carbon source is dissolved in molybdenum foil
Surface, gaseous carbon source selects methane in embodiment, and protective gas is argon gas and hydrogen.Protective gas is with the velocity ratio of methane
Ar:H2:CH4=20:1:1.
After methane is passed through end, respectively by S sources and MoO3Heating zone I and heating zone II where source start simultaneously at and are warming up to
175 DEG C and 750 DEG C, and maintain the constant temperature 30min to carry out the growth of molybdenum bisuphide.After growth terminates, rapidly by heating zone I and heating
The temperature in area II is down to room temperature to prevent two introduces a collections from continuing volatiling reaction, and in Ar:H2=10:The drop of 5 DEG C/s is controlled under 1 atmosphere
Warm speed is lowered the temperature.Substrate is taken out after chamber is cooled to room temperature, the molybdenum bisuphide-Graphene heterojunction structure that will be prepared
It is transferred to SiO2On/Si substrates.
Specifically, the transfer uses wet method shifting process：First, on film spin coating a layer thickness about 200nm PMMA
Glue, then uses FeCl3Solution falls molybdenum foil substrate etching, then different with molybdenum bisuphide-Graphene that target substrate supports PMMA
Matter structural membrane is picked up, and is finally removed PMMA with acetone and other organic solvent, and next step table can be carried out after the completion of transfer work
Levy.
The present embodiment result：S sources and MoO3Source is heated volatilization, and molybdenum foil surface is deposited under the drive of protective atmosphere, is passed through
The chemical reaction of a series of complex is crossed, it contains molybdenum and the product of sulfur-bearing is deposited in the molybdenum foil substrate surface for being dissolved with carbon and reacts shape
Into molybdenum bisuphide single or multiple lift domain；Methyl hydride catalyzed decomposition simultaneously dissolves in molybdenum foil surface, by indigenous graphite alkene most end form of lowering the temperature
Into Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure.As shown in fig. 2, it can be seen that in above-mentioned growth bar
Under part, the superficial growth of molybdenum foil substrate forms Graphene continuous film, and it is 10 μm or so to form the length of side in continuous film superficial growth
Molybdenum bisuphide domain.From Fig. 2, domain has the space further grown up.The transition metal sulfur family chemical combination prepared under the conditions of this
In thing two-dimensional material-Graphene heterojunction structure, the molybdenum bisuphide domain overwhelming majority is monoatomic layer, but is not excluded for extremely indivedual brilliant
Occurs the possibility of small area multilayer stacking inside farmland.As shown in Figure 3 a, the film of growth is transferred to 300nm SiO2/ Si substrates
On, can be by the Raman of black filled circles labeling position inside observation by light microscope to molybdenum bisuphide domain, and analysis domain
Figure, as shown in Figure 3 b, in illustration, 384cm-1And 405cm-1There is characteristic peak in place, it was demonstrated that the domain for being grown is molybdenum bisuphide
Film；In 1350cm-1、1580cm-1And 2680cm-1There is characteristic peak in place, it was demonstrated that molybdenum disulfide film is deposited below position
In graphene film, but there is certain defect.
Embodiment two
The present embodiment is with the difference of embodiment one：It is that molybdenum foil substrate is replaced by platinum foil lining by the substrate in embodiment one
Bottom, remaining technological parameter is identical with embodiment one.
The present embodiment result：As shown in figure 4, compared to embodiment one, after platinum foil substrate, molybdenum bisuphide crystal domain size
Further increase, average-size can be to 20 μm or so.This is mainly platinum foil substrate catalytic effect compared with the molybdenum foil that embodiment one is selected
Effect more preferably, promotes the monolayer growth of molybdenum bisuphide.The film of preparation is transferred to SiO2On/Si substrates, molybdenum bisuphide is analyzed
The Mapping figures of characteristic peak positions, as shown in Figure 5, it was demonstrated that molybdenum bisuphide domain is in the Graphene continuous film superficial growth uniformity
Preferably.
Embodiment three
The present embodiment is with the difference of embodiment one：It is that S sources are replaced by Se sources by source material I in embodiment one, and will
The final temperature of correspondence warm area heating zone I increases to 275 DEG C, and remaining technological parameter is identical with embodiment one.
The present embodiment result：As shown in fig. 6, compared to embodiment one, behind Se sources, two selenizing molybdenum average-sizes are 20
μm or so.This is far below S sources mainly due to Se sources degree of volatility so that enough gaseous state Se be difficult to diffuse to substrate surface with
Gaseous state MoO3Occur sufficiently to chemically react and be deposited on target substrate top.As shown in Figure 7a, the film of preparation is transferred to
On SiO2/Si substrates, by observation by light microscope to selenizing molybdenum domain, analysis domain inside black filled circles labeling position
Raman schemes, as shown in Figure 7b, in illustration, 245cm-1And 291cm-1There is characteristic peak in place, it was demonstrated that the domain for being grown is two
Selenizing molybdenum film.In 1350cm-1、1580cm-1And 2680cm-1There is characteristic peak in place, it was demonstrated that two selenizing molybdenum film positions
There is graphene film in lower section, but there is certain defect.
Example IV
The present embodiment is with the difference of embodiment one：It is MoO by the source material II in embodiment one3Source is replaced by W sources,
The final temperature of correspondence warm area heating zone II is increased to 900 DEG C, by the final temperature increase of substrate correspondence warm area heating zone III
To 850 DEG C, remaining technological parameter is identical with embodiment one.
The present embodiment result：As shown in figure 8, compared to embodiment one, behind W sources, tungsten disulfide size and curing
Molybdenum size is suitable, but mostly diatomic layer or polyatom Rotating fields.As illustrated in fig. 9, the film transfer that will be prepared after the completion of growth
To SiO2On/Si substrates, can be by observation by light microscope to tungsten disulfide domain, and analysis domain inside black filled circles mark
The Raman figures of position are noted, as shown in figure 9b, in illustration, 355cm-1And 419cm-1There is characteristic peak in place, it was demonstrated that grown
Domain is tungsten disulfide film；In 1350cm-1、1580cm-1And 2680cm-1There is characteristic peak in place, it was demonstrated that molybdenum disulfide film institute
There is graphene film below position, but there is certain defect.
Comparative example one
The present embodiment is with the difference of embodiment one：By the rate of temperature fall of temperature-fall period in embodiment one be changed to 10 DEG C/
Min, remaining technological parameter is identical with embodiment one.
The present embodiment result：Compared to embodiment one, change after rate of temperature fall, substrate surface separates out a large amount of unformed
Carbon, the presence of Graphene is not found.As shown in Figure 10 a, the film of preparation is transferred to SiO after the completion of growth2/ Si substrates
On, can be by observation by light microscope to tungsten disulfide domain, and to domain inside (grey filled circles) and outside (solid black
Circle) labeling position carries out Raman signs, as shown in Figure 10 b, 10c, 355cm-1And 419cm-1There is characteristic peak in place, it was demonstrated that give birth to
Domain long is tungsten disulfide film；In 1350cm-1There is an obvious broad peak in place, it was demonstrated that molybdenum disulfide film position
Lower section there are a large amount of agraphitic carbons.
The comparative example one illustrates, when rate of temperature fall is changed to 10 DEG C/min, to will be unable to generate Transition-metal dichalcogenide two
Dimension material-Graphene heterojunction structure.
Comparative example two
The present embodiment is with the difference of embodiment one：Embodiment one is passed through the order of methane and the two introduces a collection materials that heat up
Exchange, i.e., be first passed through methane and insulation annealing after growth molybdenum bisuphide, remaining technological parameter is identical with embodiment one.
The present embodiment result：As shown in figure 11, compared to embodiment one, on molybdenum foil substrate first growing molybdenum bisuphide causes
Its Enhancing Nucleation Density increases, and crystal domain size is decreased to 5 μm or so, and domain pattern is partial to circle, illustrates that domain has more lacking
Fall into.This be probably because there is certain metal step in molybdenum foil surface, molybdenum bisuphide preferentially in step or defective locations forming core, its
Enhancing Nucleation Density increases, and because source material is limited, therefore crystal domain size is decreased compared with embodiment one and self-defect increases.
After being subsequently passed methane and cycle annealing, methane there is also certain corrasion to molybdenum bisuphide domain, and further increase is brilliant
Farmland defect, single/multiple stone can not be grown in molybdenum bisuphide with molybdenum foil interface and by the molybdenum foil surface that molybdenum bisuphide is covered
Black alkene domain or film.
According to the comparative example two, illustrate to be passed through methane and exchanged with the order of the two introduces a collection materials that heat up that heterojunction structure can be influenceed
Size, Enhancing Nucleation Density and defect concentration etc..
Comparative example three
The present embodiment is with the difference of embodiment one：It is that molybdenum foil substrate is replaced by not and possesses molten by substrate in embodiment one
Carbon ability SiO2Substrate, remaining technological parameter is identical with embodiment one.
The present embodiment result：Compared to embodiment one, from the SiO for not possessing molten carbon ability2After substrate, substrate surface is only
Molybdenum bisuphide domain is formd, the presence of Graphene or agraphitic carbon is not found thereunder.The film that will be prepared turns
Move on SiO2/Si substrates, analysis molybdenum bisuphide characteristic peak positions and Graphene position Raman collection of illustrative plates, such as Figure 12 a, 12b,
Shown in 12c, 245cm-1And 291cm-1There is characteristic peak in place, it was demonstrated that molybdenum bisuphide domain quality is higher, but is not found graphite
Alkene or the corresponding characteristic peak of agraphitic carbon.
In sum, the present invention provides a kind of original of Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure
Position growing method, by first in Grown Transition-metal dichalcogenide two-dimensional material, then by controlling cooling speed
The single/multiple domain of method indigenous graphite alkene or continuous film of rate, so as to prepare to form transition metal sulfur family in substrate surface
Compound two-dimensional material-Graphene heterojunction structure.The method is good by controlling growth parameter(s) stackability can be prepared on substrate
Good Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure, this method preparation condition is simple, low cost, growth
The window of required conditional parameter is wider, reproducible, is to prepare Transition-metal dichalcogenide two-dimensional material-Graphene the later stage
Related electronic device lays a good foundation.So, the present invention effectively overcomes various shortcoming of the prior art and has height
Degree industrial utilization.
Above-described, only presently preferred embodiments of the present invention is not limited to the scope of the present invention, it is of the invention on
Stating embodiment can also make a variety of changes.What i.e. every claims and description according to the present patent application were made
Simply, equivalence changes and modification, fall within the claims of patent of the present invention.Of the invention not detailed description is
Routine techniques content.
Claims (10)
1. a kind of growth in situ method of Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure, its feature exists
In, including：
Step A：Substrate, source material I, source material II and carbon source are provided respectively, the substrate are heated up, in protective gas
The carbon source is set to be dissolved into the surface of the substrate under atmosphere, the source material I and source material II are heated volatilization respectively, further
Deposited on the surface of the substrate for being dissolved with carbon and react a kind of Transition-metal dichalcogenide two-dimensional material of generation；And
Step B：The substrate is controlled to be lowered the temperature with certain rate of temperature fall, in Transition-metal dichalcogenide two dimension material
The interface indigenous graphite alkene with the substrate is expected, so as to obtain a kind of Transition-metal dichalcogenide two-dimensional material-Graphene
Heterojunction structure.
2. growth in situ method according to claim 1, it is characterised in that the step A is specifically included：
A1：Cleaning substrate, weighs the source material I of certain mass with source material II respectively；
A2：The substrate, source material I, source material II are respectively put into each heating zone of heated type chemical vapor deposition chamber
In, it is 550-1100 DEG C to keep the substrate temperature, after being passed through carbon source, high annealing 1min~60min；And
A3：The source material I is separately heated to 100~300 DEG C and 500~950 DEG C with the source material II, while being passed through guarantor
Shield gas 5min~60min, generates the Transition-metal dichalcogenide two-dimensional material.
3. growth in situ method according to claim 2, it is characterised in that the substrate is selected from possesses certain molten carbon ability
Metal or alloy.
4. growth in situ method according to claim 3, it is characterised in that the substrate is selected from Co, Ni, Pt, Mo, W, Pd
Or the one kind in Ta.
5. growth in situ method according to claim 2, it is characterised in that the source material I is selected from containing S, Se, Te
One or more in gas, liquid, solid state source, the source material II is selected from the gas, liquid, solid state source containing Mo, W, Ta, Ga, Sn, Re
One or more.
6. growth in situ method according to claim 2, it is characterised in that the carbon source is selected from carbon containing gas, liquid, solid source
In one or more.
7. growth in situ method according to claim 2, it is characterised in that the step B is specifically included：
Heating zone where the substrate is controlled under the atmosphere of the protective gas is entered with the rate of temperature fall of 1 DEG C/s-20 DEG C/s
Row cooling, in the temperature-fall period, separates out in the Transition-metal dichalcogenide two-dimensional material with the interface of the substrate
Graphene.
8. growth in situ method according to claim 7, it is characterised in that the protective gas be argon gas with hydrogen or
The mixed gas of helium and hydrogen, the volume ratio of the mixed gas is 0.2:1~20:1.
9. a kind of Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure, it is characterised in that the transition metal
Chalcogenide two-dimensional material-Graphene heterojunction structure is using the growth in situ according to any one in claim 1-8
It is prepared by method.
10. Transition-metal dichalcogenide two-dimensional material-Graphene heterojunction structure according to claim 9, its feature exists
In the Transition-metal dichalcogenide two-dimensional material is individual layer domain, multilayer domain or continuous film, and the Graphene is
Individual layer domain, multilayer domain or continuous film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611019332.XA CN106756871B (en) | 2016-11-14 | 2016-11-14 | A kind of Transition-metal dichalcogenide two-dimensional material-graphene heterojunction structure and its growth in situ method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611019332.XA CN106756871B (en) | 2016-11-14 | 2016-11-14 | A kind of Transition-metal dichalcogenide two-dimensional material-graphene heterojunction structure and its growth in situ method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106756871A true CN106756871A (en) | 2017-05-31 |
| CN106756871B CN106756871B (en) | 2019-04-05 |
Family
ID=58969814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611019332.XA Active CN106756871B (en) | 2016-11-14 | 2016-11-14 | A kind of Transition-metal dichalcogenide two-dimensional material-graphene heterojunction structure and its growth in situ method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106756871B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107574475A (en) * | 2017-07-11 | 2018-01-12 | 电子科技大学 | A kind of HfS2The preparation method of single crystal nanoplate |
| CN109019569A (en) * | 2017-06-08 | 2018-12-18 | 中国科学院金属研究所 | High-quality graphene/two-dimensional metallic carbide crystalline vertical heterojunction structure material and preparation method thereof |
| CN110047912A (en) * | 2019-05-24 | 2019-07-23 | 合肥本源量子计算科技有限责任公司 | A kind of vertical heterojunction material and chemical vapor deposition unit |
| CN110607515A (en) * | 2019-08-27 | 2019-12-24 | 深圳大学 | Preparation method of two-dimensional metal organic framework material and product |
| KR20210147179A (en) * | 2020-05-28 | 2021-12-07 | 성균관대학교산학협력단 | Method for producing transition metal dichalcogenide-graphene hetero junction composite using plasma |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140245946A1 (en) * | 2013-03-01 | 2014-09-04 | Massachusetts Institute Of Technology | Synthesis and Transfer of Transition Metal Disulfide Layers on Diverse Surfaces |
| CN104694927A (en) * | 2013-12-10 | 2015-06-10 | 成均馆大学校产业协力团 | Metal chalcogenide thin film and preparing method thereof |
| CN106024861A (en) * | 2016-05-31 | 2016-10-12 | 天津理工大学 | Two-dimensional black phosphorus/transitional metal chalcogenide heterojunction device and preparation method therefor |
-
2016
- 2016-11-14 CN CN201611019332.XA patent/CN106756871B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140245946A1 (en) * | 2013-03-01 | 2014-09-04 | Massachusetts Institute Of Technology | Synthesis and Transfer of Transition Metal Disulfide Layers on Diverse Surfaces |
| CN104694927A (en) * | 2013-12-10 | 2015-06-10 | 成均馆大学校产业协力团 | Metal chalcogenide thin film and preparing method thereof |
| CN106024861A (en) * | 2016-05-31 | 2016-10-12 | 天津理工大学 | Two-dimensional black phosphorus/transitional metal chalcogenide heterojunction device and preparation method therefor |
Non-Patent Citations (2)
| Title |
|---|
| 冯冯 等: "准二维金属硫属化合物类石墨烯结构的化学合成与组装", 《中国科学》 * |
| 陈亚玲 等: "水热合成二硫化钨_石墨烯复合材料及其氧还原性能", 《无机化学学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109019569A (en) * | 2017-06-08 | 2018-12-18 | 中国科学院金属研究所 | High-quality graphene/two-dimensional metallic carbide crystalline vertical heterojunction structure material and preparation method thereof |
| CN109019569B (en) * | 2017-06-08 | 2021-05-28 | 中国科学院金属研究所 | High-quality graphene/two-dimensional metal carbide crystal vertical heterostructure material and preparation method thereof |
| CN107574475A (en) * | 2017-07-11 | 2018-01-12 | 电子科技大学 | A kind of HfS2The preparation method of single crystal nanoplate |
| CN107574475B (en) * | 2017-07-11 | 2019-10-01 | 电子科技大学 | A kind of HfS2The preparation method of single crystal nanoplate |
| CN110047912A (en) * | 2019-05-24 | 2019-07-23 | 合肥本源量子计算科技有限责任公司 | A kind of vertical heterojunction material and chemical vapor deposition unit |
| CN110607515A (en) * | 2019-08-27 | 2019-12-24 | 深圳大学 | Preparation method of two-dimensional metal organic framework material and product |
| CN110607515B (en) * | 2019-08-27 | 2022-05-10 | 深圳大学 | Preparation method of two-dimensional metal organic framework material and product |
| KR20210147179A (en) * | 2020-05-28 | 2021-12-07 | 성균관대학교산학협력단 | Method for producing transition metal dichalcogenide-graphene hetero junction composite using plasma |
| KR102434399B1 (en) | 2020-05-28 | 2022-08-19 | 성균관대학교산학협력단 | Method for producing transition metal dichalcogenide-graphene hetero junction composite using plasma |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106756871B (en) | 2019-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106756871B (en) | A kind of Transition-metal dichalcogenide two-dimensional material-graphene heterojunction structure and its growth in situ method | |
| Geng et al. | Graphene single crystals: size and morphology engineering | |
| Tao et al. | The effect of seed layer on morphology of ZnO nanorod arrays grown by hydrothermal method | |
| CN103194729B (en) | The preparation method of metal chalcogenide film | |
| CN104726845B (en) | The preparation method of the upper graphene nanobelts of h-BN | |
| CN104058458B (en) | Preparation method of high-quality single-layer and double-layer controllable molybdenum disulfide | |
| CN109371381B (en) | Method for preparing single-layer molybdenum sulfide/tungsten sulfide in-plane heterojunction by low-temperature one-step method | |
| CN104036878B (en) | A kind of preparation method of graphene and CNT three-dimensional structure material | |
| CN104562195B (en) | The growing method of Graphene | |
| CN110040725B (en) | Method for rapidly preparing high-quality graphene film with uniform layer number | |
| CN103774113B (en) | A kind of method preparing hexagonal boron nitride film | |
| CN110416065B (en) | Preparation method of molybdenum disulfide/tungsten diselenide vertical heterojunction | |
| CN107287578B (en) | A kind of chemical gas-phase deposition process for preparing of a wide range of uniformly double-deck molybdenum disulfide film | |
| CN104538288B (en) | A kind of device and method of direct growth atomic scale two-dimensional semiconductor hetero-junctions | |
| CN102874801A (en) | Preparation method for graphene | |
| CN107540245B (en) | In-situ direct preparation method of graphene optical fiber | |
| CN111146079B (en) | Synthesis and application of two-dimensional metal-semiconductor Van der Waals heterojunction array | |
| CN112663144B (en) | Two-dimensional In 2 S 3 Preparation method of/SnS heterojunction crystalline material | |
| CN109437124B (en) | Method for synthesizing single-layer transition metal chalcogenide | |
| CN111850509A (en) | Method for preparing transition metal chalcogenide planar heterojunction by in-situ control method | |
| CN104746144A (en) | Preparation method of stannic disulfide monocrystal nanosheet | |
| US20170081782A1 (en) | Transfer-free method for forming graphene layer | |
| CN108314019A (en) | A kind of preparation method of the uniform large-area high-quality graphene film of the number of plies | |
| CN110010449B (en) | Method for efficiently preparing one-dimensional carbon nanotube/two-dimensional transition metal chalcogenide heterojunction | |
| CN113410287B (en) | Two-dimensional SnSe-SnSe 2 P-n heterojunction and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |